JPH07304723A - Acylcarbamate having hydroxy group and production thereof - Google Patents

Abstract

PURPOSE:To obtain a low-molecular weight compound having one hydroxy group and one acylcarbamate group in a molecule useful for introducing an acylcarbamate group into other material. CONSTITUTION:A compound of formula I (R<1> is a 2-12C alkylene which may 1-8C alkylene, an arylene or an alkenylene; R<3> is a 1-18C alkyl or aryl which may contain 0, e.g. N-[2-(2-hydroxyethoxycarbonyl)-benzoyl] carbamic acid ethyl ester. The compound is obtained by reacting an N-alkoxycarbonyl cyclic imide of formula II with a diol of formula III at an equivalent ratio of 1: <=3, preferably in the presence of a basic catalyst. The compound of formula I can be obtained in a high yield by suppressing production of a compound having diol whose both ends are acylcarbamated using the method.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an acyl carbamate having a hydroxyl group, that is, a compound having one hydroxyl group and one acyl carbamate group in the molecule, and a method for producing the same.

[0002]

2. Description of the Related Art Acyl carbamate groups are known to be highly reactive as compared with ordinary ester groups, such as undergoing an exchange reaction with a hydroxyl group even in the absence of a catalyst. If such an acyl carbamate group can be easily introduced into various materials such as polymers, the development of highly functional paints and adhesives will be very promising.
To introduce an acyl carbamate group into another material,
A compound having an acyl carbamate group and a functional group having active hydrogen, particularly a hydroxyl group in the same molecule is desired.

Japanese Unexamined Patent Publication (Kokai) No. 61-1653 discloses a method for producing a polyacyl urethane obtained by reacting an N-alkoxycarbonyl cyclic imide with a so-called polyol. The polyacyl urethane obtained here has a large number of acyl carbamate groups pendent from the polyol main chain through hydroxyl groups.

The publication also discloses a method of leaving a part of the hydroxyl groups of the polyol, but the resulting polymer has an excessively large functional group equivalent and is not suitable for introduction into other materials. Also, when this method is applied to a diol in order to reduce the functional group equivalent, a large amount of a compound in which two hydroxyl groups in the diol are both converted to an acyl carbamate group is produced as a by-product, and an acyl carbamate group is formed. A compound having one hydroxyl group and one hydroxyl group in the same molecule is hardly obtained.

[0005]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned conventional problems, and an object thereof is to provide an acylcarbamate group useful for introducing an acylcarbamate group into another material. It is to provide a compound having one hydroxyl group and one hydroxyl group in the same molecule.

[0006]

The present invention is based on the formula

[0007]

[Chemical 4]

[In the formula, R ¹ is an alicyclic ring, an aromatic ring and an alkylene group having 2 to 12 carbon atoms which may contain an oxygen atom, and R ² is 1 to 8 carbon atoms, preferably 2 to 6 carbon atoms. It is an alkylene group, an arylene group or an alkenylene group, and R ³ has 1 to 18 carbon atoms which may contain an oxygen atom, preferably 2
~ 8 is an alkyl group or an aryl group. ] An acyl carbamate represented by the above formula is provided, whereby the above object is achieved.

In a preferred embodiment of the invention R ¹ is the residue of a diol. "Residue of diol" means 2 from diol
The divalent group remaining after the removal of individual hydroxyl groups. The diol that can be used in the present invention is not particularly limited as long as its residue is an alicyclic ring, an aromatic ring or an alkylene group having 2 to 12 carbon atoms which may contain an oxygen atom.

Specific examples of diols preferably used in the present invention include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol and 1,4. -Pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol,
1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-octadecanediol, 1,8-octadecanediol, 2,5-dimethyl-2,5-hexanediol, 2, Of alkanediols such as 2-dimethyl-1,3-propanediol and 2,5-diethyl-2,5-hexanediol; alkendiols such as 2-butenediol and 3-hexenediol; of diethylene glycol and triethylene glycol Such ether bond-containing diols; ester group-containing diols such as dihydroxyethyl carbonate; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol,
Alicyclic group-containing diols such as 1,2-cyclopentanediol, 1,2-cyclooctanediol, 1,4-cyclooctanediol, 1,5-cyclooctenediol and 4,4'-dicyclohexanediol; Examples include aryl group-containing diols such as 1,2-benzenedimethanol and dibenzyl alcohol.

In the present invention, R ² is preferably a divalent hydrocarbon group such as an alkylene group, an arylene group or an alkenylene group. R ² preferably has 1 to 8, especially 2 to 6 carbon atoms. Particularly preferred in the present invention
Specific examples of R ² include ethylene group, 1,2-phenylene group, 1,2-
A cyclohexylene group and an ethynyl group are mentioned.

In the present invention, R ³ is preferably an alkyl group or aryl group which may contain oxygen. R ³
Preferably has 1 to 18, especially 2 to 8 carbon atoms.

Specific examples of R ³ include a methyl group, an ethyl group and n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, nonyl group, decanyl group, stearyl group, benzyl group, allyl group Hydrocarbon groups such as propargyl group and phenyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group,
Hexyloxyethyl group, methoxyethyloxy group, ethoxyethyloxyethyl group and butoxyethyloxyethyl group are mentioned.

The compounds of the present invention are specifically illustrated in Tables 1 to 3 below.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

[Table 3]

The acyl carbamate having a hydroxyl group of the present invention has the formula

[0019]

[Chemical 5]

[In the formula, R ² and R ³ have the same meanings as described above. ] N-alkoxycarbonyl cyclic imide represented by the formula

[0021]

[Chemical 6]

[In the formula, R ¹ has the same meaning as described above. ] The above-mentioned diol represented by the above formula] is reacted at an equivalent ratio of less than 1: 3. The reaction formula is shown below.

[0023]

[Chemical 7]

Table 4 below shows specific examples of N-alkoxycarbonyl cyclic imides that can be used in the method of the present invention.

[0025]

[Table 4]

These N-alkoxycarbonyl cyclic imides can be obtained by reacting a cyclic imide with a chloroformate.

In the production of the acyl carbamate of the present invention, the amount of the hydroxyl group of the diol is 3 to 8 times, preferably 5 to 8 times the amount of the cyclic imide group of the N-alkoxycarbonyl cyclic imide. It is preferable to react with N-alkoxycarbonyl cyclic imide. If the equivalent ratio of the N-alkoxycarbonyl cyclic imide and the diol exceeds 1: 3, the amount of the compound in which both ends of the diol are acylcarbamated is larger than that of the target product, and thus the target product cannot be obtained in high yield. . If this equivalent ratio is less than 1: 8, a compound in which both ends of the diol are acylcarbamated is scarcely produced, but the yield of the desired product does not increase remarkably, which is not very efficient and is not preferable.

It is preferable to use a catalyst to increase the reaction rate of the N-alkoxycarbonyl cyclic imide and the diol. A so-called basic catalyst can be used as the catalyst. As the basic catalyst, a tertiary amine or an alkali metal compound can be used. Examples of the tertiary amine include triethylamine, tributylamine, pyridine, dimethylaminopyridine, N-methylmorpholine, N-methylpiperidine, diazabicyclo- [2,2,2]-
Examples include octane.

Examples of the alkali metal compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. The amount of the above catalyst used is
0.05-15 based on N-alkoxycarbonyl cyclic imide
Mol% is preferable, more preferably 0.5 to 5 mol%
Is.

If desired, a solvent may be used. Solvents that do not have active hydrogen, specifically hydrocarbons such as heptane, benzene, toluene and xylene, halogenated hydrocarbons such as dichloroethane and o-dichlorobenzene, butyl acetate and ethyl acetate. Solvents such as ester systems such as, ethyl ketone systems such as methyl ethyl ketone and cyclohexanone, ether systems such as dioxane and tetrahydrofuran, and aprotic solvents such as dimethyl sulfoxide and dimethylformamide can be used.

Furthermore, it is preferable to carry out the reaction under heating conditions. Although the reaction temperature is not particularly limited, it is preferably 120 ° C. or lower. Excessive heating above 150 ° C. may cause side reactions, which is not preferable.

The basic operation is as follows. A N-alkoxycarbonyl cyclic imide and a diol are put into a reaction vessel, and a catalyst and / or a solvent are added if necessary. This is heated to a predetermined temperature and stirred. The reaction can be completed after a certain period of time, but it is also possible to complete the reaction after confirming the disappearance of the raw materials by a general analytical method such as gas chromatography, liquid chromatography or thin layer chromatography.

The reaction mixture is treated by a general method, and if necessary, the desired product can be obtained through purification by recrystallization or silica gel column chromatography.
The compound can be confirmed by measuring an infrared absorption spectrum (IR), a nuclear magnetic resonance spectrum (NMR) and the like.

[0034]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 A magnetic stirrer was placed in a reaction vessel equipped with a cooling tube and a nitrogen blowing tube, and 20.2 g (91.3 mmol) of N-ethoxycarbonylphthalimide and 57.0 g (913 mm of ethanediol were added thereto.
ol) and 0.4 g of triethylamine were added. 85 ° C
After heating for 2.5 hours, thin layer chromatography confirmed that N-ethoxycarbonylphthalimide had disappeared, and the reaction was completed. The reaction mixture was concentrated with a rotary evaporator, methylene chloride was added, and the mixture was washed 3 times with water. After drying the organic phase with magnesium sulfate, the solvent was distilled off with a rotary evaporator to obtain 14.9 g of a pale yellow liquid. The yield based on N-ethoxycarbonylphthalimide was 86%.

The characteristics of the obtained compound were measured using the following measuring instruments. Melting point Yanaco MP-51965 Viscosity Tokyo Keiki Co. EL, EM or EL type viscometer (20 ° C) IR JASCO FT / IR-5300 NMR Bruka ASPECT-3000 Analysis results and identified structure It shows in Table 5.

[0037]

[Table 5]

Example 2 N-ethoxycarbonylphthalimide was added under the conditions shown in Table 19.
Example 1 except reacting with 1,4-butanediol
The product was obtained in the same manner as. Table 6 shows the analysis results and the identified structure of the obtained compound.

[0039]

[Table 6]

Example 3 N-ethoxycarbonylphthalimide was added under the conditions shown in Table 19.
A product was obtained in the same manner as in Example 1 except that 1,6-hexanediol was reacted. Table 7 shows the analysis results and the identified structure of the obtained compound.

[0041]

[Table 7]

Example 4 N-ethoxycarbonylphthalimide was added under the conditions shown in Table 19.
Example 1 except reaction with 1,9-nonanediol
The product was obtained in the same manner as. Table 8 shows the analysis results and the identified structure of the obtained compound.

[0043]

[Table 8]

Example 5 N-ethoxycarbonylphthalimide was added under the conditions shown in Table 19.
A product was obtained in the same manner as in Example 1 except that the reaction was performed with 1,12-dodecanediol. Table 9 shows the analysis results and the identified structure of the obtained compound.

[0045]

[Table 9]

Example 6 N-ethoxycarbonylphthalimide was added under the conditions shown in Table 19.
A product was obtained in the same manner as in Example 1 except that 1,4-cyclohexanediol was reacted. Table 10 shows the analysis results and the identified structure of the obtained compound.

[0047]

[Table 10]

Example 7 A product was obtained in the same manner as in Example 1 except that N-ethoxycarbonylphthalimide and xylylene glycol were reacted under the conditions shown in Table 19. Table 11 shows the analysis results and the identified structure of the obtained compound.

[0049]

[Table 11]

Example 8 A product was obtained in the same manner as in Example 1 except that N-ethoxycarbonylphthalimide and neopentyl glycol were reacted under the conditions shown in Table 20. Table 12 shows the analysis results and the identified structure of the obtained compound.

[0051]

[Table 12]

Example 9 A product was obtained in the same manner as in Example 1 except that N-ethoxycarbonylphthalimide and triethylene glycol were reacted under the conditions shown in Table 20. Table 13 shows the analysis results and the identified structure of the obtained compound.

[0053]

[Table 13]

Example 10 A product was obtained in the same manner as in Example 1 except that N-phenoxyphthalimide and 1,6-hexanediol were reacted under the conditions shown in Table 20. Table 14 shows the analysis results and the identified structure of the obtained compound.

[0055]

[Table 14]

Example 11 Example 1 except that N-ethoxycarbonylsuccinimide and ethylene glycol were reacted under the conditions shown in Table 20.
The product was obtained in the same manner as. Table 15 shows the analysis results and the identified structure of the obtained compound.

[0057]

[Table 15]

Example 12 N-ethoxycarbonylsuccinimide was added under the conditions shown in Table 20.
A product was obtained in the same manner as in Example 1 except that 1,6-hexanediol was reacted. Table 16 shows the analysis results and the identified structure of the obtained compound.

[0059]

[Table 16]

Example 13 A product was obtained in the same manner as in Example 1 except that N-butoxyethyloxycarbonyl succinimide and 1,6-hexanediol were reacted under the conditions shown in Table 20. Table 17 shows the analysis results and the identified structure of the obtained compound.

[0061]

[Table 17]

Example 14 A product was obtained in the same manner as in Example 1 except that N- (2-ethylhexyloxycarbonyl) maleimide and 1,6-hexanediol were reacted under the conditions shown in Table 20. Table 18 shows the analysis results and the identified structure of the obtained compound.

[0063]

[Table 18]

[0064]

[Table 19]

[0065]

[Table 20]

Example 15 A monoacyl carbamate compound of ethanediol (N-ethoxycarbonylphthalimide and ethanediol was changed to a monoacyl carbamate compound at a temperature of 85 ° C. for 3.5 hours in dioxane using potassium t-butoxide as a catalyst. The amounts of 3) and the diacyl carbamate compound (4) produced were determined by H-NMR using benzyl alcohol as a standard.

[0067]

[Chemical 8]

The results are shown in FIG. From the result of FIG. 1, it was shown that the monoacyl carbamate compound is predominantly produced when the imide and the diol are reacted at an equivalent ratio of less than 1: 3.

[0069]

INDUSTRIAL APPLICABILITY A low molecular weight compound having one hydroxyl group and one acylcarbamate group in the molecule, which is useful for introducing an acylcarbamate group into another material, is provided. As a result, it became possible to introduce an acyl carbamate group into other than the acrylic polymer. In addition, by-products during the production were suppressed and the yield was improved.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the equivalent ratio of N-ethoxycarbonylphthalimide and ethanediol and the production amounts of ethanediol monoacyl carbamate and diacyl carbamate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07D 209/48

Claims (2)

[Claims] 1. The formula: [In the formula, R ¹ is an alicycle, an aromatic ring and an alkylene group having 2 to 12 carbon atoms which may contain an oxygen atom, and R ² is an alkylene group having 1 to 8 carbon atoms, an arylene group or an alkenylene group. And R ³ has 1 carbon atom which may include an oxygen atom.
~ 18 alkyl or aryl groups. ] The acyl carbamate shown by these. 2. The formula: [In the formula, R ² is an alkylene group having 1 to 8 carbon atoms, an arylene group or an alkenylene group, and R ³ is an alkyl group having 1 to 18 carbon atoms or an aryl group which may contain an oxygen atom. ] And an N-alkoxycarbonyl cyclic imide represented by the formula: [In the formula, R ¹ is an alicyclic ring, an aromatic ring and an alkylene group having 2 to 12 carbon atoms and optionally containing an oxygen atom. ] The method of manufacturing the acyl carbamate which has a hydroxyl group including the process of making it react with the diol shown by these in the equivalent ratio less than 1: 3.